JP5229150B2 - Fullerene derivatives - Google Patents
Fullerene derivatives Download PDFInfo
- Publication number
- JP5229150B2 JP5229150B2 JP2009178996A JP2009178996A JP5229150B2 JP 5229150 B2 JP5229150 B2 JP 5229150B2 JP 2009178996 A JP2009178996 A JP 2009178996A JP 2009178996 A JP2009178996 A JP 2009178996A JP 5229150 B2 JP5229150 B2 JP 5229150B2
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- Prior art keywords
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- fullerene derivative
- organic
- photoelectric conversion
- formula
- Prior art date
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims description 86
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 150000001875 compounds Chemical class 0.000 claims description 38
- 239000010410 layer Substances 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000012044 organic layer Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- -1 2-ethylhexyl group Chemical group 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 16
- 239000010409 thin film Substances 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 125000003118 aryl group Chemical group 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 125000003545 alkoxy group Chemical group 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 229910003472 fullerene Inorganic materials 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000003818 flash chromatography Methods 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 4
- 150000002332 glycine derivatives Chemical class 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 3
- CHAPAHNWSCYFRM-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethylamino]acetic acid Chemical compound COCCOCCNCC(O)=O CHAPAHNWSCYFRM-UHFFFAOYSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 125000003184 C60 fullerene group Chemical group 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000012230 colorless oil Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 2
- FFOPEPMHKILNIT-UHFFFAOYSA-N Isopropyl butyrate Chemical compound CCCC(=O)OC(C)C FFOPEPMHKILNIT-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- NVDGEKCUPOGITJ-UHFFFAOYSA-N benzyl 2-[2-(2-hydroxyethoxy)ethyl-[(2-methylpropan-2-yl)oxycarbonyl]amino]acetate Chemical compound OCCOCCN(C(=O)OC(C)(C)C)CC(=O)OCC1=CC=CC=C1 NVDGEKCUPOGITJ-UHFFFAOYSA-N 0.000 description 2
- ODMZKNNPNGFREP-UHFFFAOYSA-N benzyl 2-[2-(2-methoxyethoxy)ethyl-[(2-methylpropan-2-yl)oxycarbonyl]amino]acetate Chemical compound COCCOCCN(C(=O)OC(C)(C)C)CC(=O)OCC1=CC=CC=C1 ODMZKNNPNGFREP-UHFFFAOYSA-N 0.000 description 2
- PLVDMZWIKRSGFR-UHFFFAOYSA-N benzyl 2-[2-(2-methoxyethoxy)ethylamino]acetate Chemical compound COCCOCCNCC(=O)OCC1=CC=CC=C1 PLVDMZWIKRSGFR-UHFFFAOYSA-N 0.000 description 2
- JHVLLYQQQYIWKX-UHFFFAOYSA-N benzyl 2-bromoacetate Chemical compound BrCC(=O)OCC1=CC=CC=C1 JHVLLYQQQYIWKX-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
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- 238000007756 gravure coating Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- FSWMHORGNFRJJC-UHFFFAOYSA-N 2-(methoxymethylamino)acetic acid Chemical compound COCNCC(O)=O FSWMHORGNFRJJC-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- CMSGUKVDXXTJDQ-UHFFFAOYSA-N 4-(2-naphthalen-1-ylethylamino)-4-oxobutanoic acid Chemical compound C1=CC=C2C(CCNC(=O)CCC(=O)O)=CC=CC2=C1 CMSGUKVDXXTJDQ-UHFFFAOYSA-N 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 1
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- PAAZCQANMCYGAW-UHFFFAOYSA-N acetic acid;2,2,2-trifluoroacetic acid Chemical compound CC(O)=O.OC(=O)C(F)(F)F PAAZCQANMCYGAW-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical group C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- AQNQQHJNRPDOQV-UHFFFAOYSA-N bromocyclohexane Chemical compound BrC1CCCCC1 AQNQQHJNRPDOQV-UHFFFAOYSA-N 0.000 description 1
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 125000006371 dihalo methyl group Chemical group 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- YZASAXHKAQYPEH-UHFFFAOYSA-N indium silver Chemical compound [Ag].[In] YZASAXHKAQYPEH-UHFFFAOYSA-N 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000001254 matrix assisted laser desorption--ionisation time-of-flight mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- 125000006372 monohalo methyl group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006610 n-decyloxy group Chemical group 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000006609 n-nonyloxy group Chemical group 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000004953 trihalomethyl group Chemical group 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/58—[b]- or [c]-condensed
- C07D209/70—[b]- or [c]-condensed containing carbocyclic rings other than six-membered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/152—Fullerenes
- C01B32/156—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/94—[b, c]- or [b, d]-condensed containing carbocyclic rings other than six-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/06—Peri-condensed systems
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
- H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Description
本発明は、フラーレン誘導体及びそれを用いた有機光電変換素子に関する。 The present invention relates to a fullerene derivative and an organic photoelectric conversion device using the fullerene derivative.
電荷（電子、ホール）輸送性を有する有機半導体材料は、有機光電変換素子（有機太陽電池、光センサー等）等への適用が検討されており、例えば、フラーレン誘導体を用いた有機太陽電池が検討されている。フラーレン誘導体としては、例えば、[６，６]−フェニルＣ６１−酪酸メチルエステル（以下、[６０]−ＰＣＢＭということがある。）が知られている（非特許文献１参照）。 Application of organic semiconductor materials having charge (electron, hole) transport properties to organic photoelectric conversion elements (organic solar cells, photosensors, etc.) has been studied. For example, organic solar cells using fullerene derivatives are considered. Has been. As a fullerene derivative, for example, [6,6] -phenyl C61-butyric acid methyl ester (hereinafter sometimes referred to as [60] -PCBM) is known (see Non-Patent Document 1).
しかし、[６０]−ＰＣＢＭを含む有機光電変換素子は、Ｖｏｃ（開放端電圧）が必ずしも十分でないという問題点がある。 However, the organic photoelectric conversion element including [60] -PCBM has a problem that Voc (open end voltage) is not always sufficient.
そこで、本発明は、Ｖｏｃ（開放端電圧）が高い有機光電変換素子を提供することを目的とする。 Then, an object of this invention is to provide an organic photoelectric conversion element with a high Voc (open end voltage).
即ち、本発明は第一に、式（１）で表される構造を有するフラーレン誘導体を提供する。
[式中、Ｒは１価の有機基を表す。ｒは０〜４の整数を表す。]
That is, the present invention first provides a fullerene derivative having a structure represented by the formula (1).
[Wherein, R represents a monovalent organic group. r represents an integer of 0 to 4. ]
本発明は第二に、前記フラーレン誘導体と電子供与性化合物とを含む組成物を提供する。 The present invention secondly provides a composition comprising the fullerene derivative and an electron donating compound.
本発明は第三に、電子供与性化合物が高分子化合物である前記組成物を提供する。 Thirdly, the present invention provides the above composition, wherein the electron donating compound is a polymer compound.
本発明は第四に、陽極と、陰極と、該陽極と該陰極との間に前記フラーレン誘導体を含む層を有する有機光電変換素子を提供する。 Fourthly, the present invention provides an organic photoelectric conversion device having an anode, a cathode, and a layer containing the fullerene derivative between the anode and the cathode.
本発明は第五に、陽極と、陰極と、該陽極と該陰極との間に前記組成物を含む層を有する有機光電変換素子を提供する。 Fifthly, the present invention provides an organic photoelectric conversion device having an anode, a cathode, and a layer containing the composition between the anode and the cathode.
本発明は第六に、陽極と、陰極と、該陽極と該陰極との間に活性層を有する有機光電変換素子であって、前記フラーレン誘導体と溶媒とを含む溶液を該陽極又は該陰極上に塗布して有機層を形成し、次いで、該有機層を加熱して該活性層を形成することを特徴とする有機光電変換素子を提供する。 Sixth, the present invention relates to an organic photoelectric conversion device having an anode, a cathode, and an active layer between the anode and the cathode, the solution containing the fullerene derivative and a solvent on the anode or the cathode. The organic photoelectric conversion element is characterized in that it is applied to form an organic layer, and then the organic layer is heated to form the active layer.
本発明は第七に、陽極と、陰極と、該陽極と該陰極との間に活性層を有する有機光電変換素子であって、前記組成物と溶媒とを含む溶液を該陽極又は該陰極上に塗布して有機層を形成し、次いで、該有機層を加熱して該活性層を形成することを特徴とする有機光電変換素子を提供する。 Seventh, the present invention provides an organic photoelectric conversion element having an anode, a cathode, and an active layer between the anode and the cathode, the solution containing the composition and a solvent being placed on the anode or the cathode. The organic photoelectric conversion element is characterized in that it is applied to form an organic layer, and then the organic layer is heated to form the active layer.
本発明のフラーレン誘導体を含む層を有する有機光電変換素子は、Ｖｏｃ（開放端電圧）が高くなるため、本発明は極めて有用である。 Since the organic photoelectric conversion element having a layer containing the fullerene derivative of the present invention has a high Voc (open end voltage), the present invention is extremely useful.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
＜フラーレン誘導体＞
本発明のフラーレン誘導体は式（１）で表される構造を有する。前記式（１）中のＲは、１価の有機基を表す。１価の有機基としては、アルキル基、アルコキシ基、アリール基、ハロゲン基、１価の複素環基、式（３）で表される基であるか又はエステル構造を有する基であることが好ましい。
<Fullerene derivative>
The fullerene derivative of the present invention has a structure represented by the formula (1). R in the formula (1) represents a monovalent organic group. The monovalent organic group is preferably an alkyl group, an alkoxy group, an aryl group, a halogen group, a monovalent heterocyclic group, a group represented by the formula (3), or a group having an ester structure. .
式（１）中、Ｒで表されるアルキル基は、炭素数が通常１〜２０であり、直鎖状でも分岐状でもよく、シクロアルキル基でもよい。アルキル基の具体例としては、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｔｅｒｔ−ブチル基、ｓｅｃ−ブチル基、３−メチルブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、２−エチルヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ラウリル基が挙げられる。前記アルキル基中の水素原子はハロゲン原子で置換されていてもよく、具体的には、モノハロメチル基、ジハロメチル基、トリハロメチル基、ペンタハロエチル基があげられる。ハロゲン原子の中では、フッ素原子で置換されていることが好ましい。フッ素原子で水素原子が置換されたアルキル基の具体例としては、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロブチル基、パーフルオロヘキシル基、パーフルオロオクチル基が挙げられる。 In formula (1), the alkyl group represented by R usually has 1 to 20 carbon atoms, and may be linear or branched, or a cycloalkyl group. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, sec-butyl group, 3-methylbutyl group, n -Pentyl group, n-hexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group can be mentioned. The hydrogen atom in the alkyl group may be substituted with a halogen atom, and specific examples include a monohalomethyl group, a dihalomethyl group, a trihalomethyl group, and a pentahaloethyl group. Of the halogen atoms, it is preferably substituted with a fluorine atom. Specific examples of the alkyl group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.
式（１）中、Ｒで表されるアルコキシ基は、炭素数が通常１〜２０であり、直鎖状でも分岐状でもよく、シクロアルキルオキシ基であってもよい。アルコキシ基の具体例としては、メトキシ基、エトキシ基、ｎ−プロピルオキシ基、ｉ−プロピルオキシ基、ｎ−ブトキシ基、ｉ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ｎ−ペンチルオキシ基、ｎ−ヘキシルオキシ基、シクロヘキシルオキシ基、ｎ−ヘプチルオキシ基、ｎ−オクチルオキシ基、２−エチルヘキシルオキシ基、ｎ−ノニルオキシ基、ｎ−デシルオキシ基、３，７−ジメチルオクチルオキシ基、ｎ−ラウリルオキシ基が挙げられる。前記アルコキシ基中の水素原子はハロゲン原子で置換されていてもよい。ハロゲン原子の中では、フッ素原子で置換されていることが好ましい。フッ素原子で水素原子が置換されたアルコキシ基の具体例としては、トリフルオロメトキシ基、ペンタフルオロエトキシ基、パーフルオロブトキシ基、パーフルオロヘキシルオキシ基、パーフルオロオクチルオキシ基が挙げられる。 In formula (1), the alkoxy group represented by R usually has 1 to 20 carbon atoms, may be linear or branched, and may be a cycloalkyloxy group. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propyloxy group, i-propyloxy group, n-butoxy group, i-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy. Group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, 3,7-dimethyloctyloxy group, n -Lauryloxy group is mentioned. A hydrogen atom in the alkoxy group may be substituted with a halogen atom. Of the halogen atoms, it is preferably substituted with a fluorine atom. Specific examples of the alkoxy group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group.
式（１）中、Ｒで表されるアリール基は、炭素数が通常６〜６０であり、置換基を有していてもよい。アリール基が有している置換基としては、炭素数１〜２０の直鎖状、分岐状のアルキル基又は炭素数１〜２０のシクロアルキル基、炭素数１〜２０の直鎖状、分岐状のアルキル基又は炭素数１〜２０のシクロアルキル基をその構造中に含むアルコキシ基があげられる。アリール基の具体例としては、フェニル基、Ｃ1〜Ｃ12アルコキシフェニル基（Ｃ1〜Ｃ12は、炭素数１〜１２であることを示す。以下も同様である。）、Ｃ1〜Ｃ12アルキルフェニル基、１−ナフチル基、２−ナフチル基が挙げられ、炭素数６〜２０のアリール基が好ましく、Ｃ1〜Ｃ12アルコキシフェニル基、Ｃ1〜Ｃ12アルキルフェニル基がより好ましい。前記アリール基中の水素原子はハロゲン原子で置換されていてもよい。ハロゲン原子の中では、フッ素原子で置換されていることが好ましい。 In formula (1), the aryl group represented by R usually has 6 to 60 carbon atoms and may have a substituent. Examples of the substituent that the aryl group has include a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, a linear or branched chain having 1 to 20 carbon atoms. Or an alkoxy group containing a cycloalkyl group having 1 to 20 carbon atoms in its structure. Specific examples of the aryl group include a phenyl group, a C 1 to C 12 alkoxyphenyl group (C 1 to C 12 represents 1 to 12 carbon atoms, and the same applies to the following), C 1 to C. Examples thereof include a 12 alkylphenyl group, a 1-naphthyl group, and a 2-naphthyl group, preferably an aryl group having 6 to 20 carbon atoms, and more preferably a C 1 to C 12 alkoxyphenyl group and a C 1 to C 12 alkylphenyl group. A hydrogen atom in the aryl group may be substituted with a halogen atom. Of the halogen atoms, it is preferably substituted with a fluorine atom.
式（１）中、Ｒで表されるハロゲン基としては、フルオロ基、クロロ基、ブロモ基、ヨード基が挙げられる。 In the formula (1), examples of the halogen group represented by R include a fluoro group, a chloro group, a bromo group, and an iodo group.
式（１）中、Ｒで表される１価の複素環基としては、１価の芳香族複素環基が好ましい。具体的には、チェニル基、ピリジル基、フリル基、ピペリジル基、キノリル基、イソキノリル基、ピロリル基が挙げられる。 In the formula (1), the monovalent heterocyclic group represented by R is preferably a monovalent aromatic heterocyclic group. Specific examples include a chenyl group, a pyridyl group, a furyl group, a piperidyl group, a quinolyl group, an isoquinolyl group, and a pyrrolyl group.
式（１）中、Ｒで表されるエステル構造を有する基としては、具体的には、酪酸メチルエステルを有する基、酪酸ｎ−ブチルエステルを有する基、酪酸イソプロピルエステルを有する基、酪酸３−エチルチオフェンエステルを有する基が挙げられる。
エステル構造を有する基の一態様は、式（４）で表される基である。
[式中、ｓは０〜１０の整数を表す。ｑは０〜１０の整数を表す。]
In the formula (1), as the group having an ester structure represented by R, specifically, a group having butyric acid methyl ester, a group having butyric acid n-butyl ester, a group having butyric acid isopropyl ester, butyric acid 3- And groups having an ethylthiophene ester.
One embodiment of a group having an ester structure is a group represented by Formula (4).
[Wherein, s represents an integer of 0 to 10. q represents an integer of 0 to 10. ]
式（１）中、Ｒで表される１価の有機基は、式（３）で表される基であってもよい。フラーレン誘導体の溶解性の観点からは、Ｒは式（３）で表される基が好ましい。
[式中、ｍは１〜６の整数を、ｎは１〜４の整数を、ｐは０〜５の整数を表す。−(ＣＨ２−)ｍ−Ｏ−で表される構造が複数個ある場合、それらの構造におけるｍは、同一の数値であっても相異なる数値であってもよい。]
In formula (1), the monovalent organic group represented by R may be a group represented by formula (3). From the viewpoint of solubility of the fullerene derivative, R is preferably a group represented by the formula (3).
[Wherein, m represents an integer of 1 to 6, n represents an integer of 1 to 4, and p represents an integer of 0 to 5. When there are a plurality of structures represented by — (CH 2 —) m —O—, m in these structures may be the same numerical value or different numerical values. ]
式（３）において、原料の入手の行いやすさの観点からは、ｍは２が好ましい。電荷輸送性の観点からは、ｐは０〜３の整数が好ましい。 In the formula (3), m is preferably 2 from the viewpoint of easy availability of raw materials. From the viewpoint of charge transportability, p is preferably an integer of 0 to 3.
式（１）において、ｒは０〜４の整数を表す。 In the formula (1), r represents an integer of 0 to 4.
本発明のフラーレン誘導体は、式（１）で表される構造を１〜４個有することが好ましい。合成の容易さの観点からは、式（１）で表される構造を１個又は２個有することがより好ましい。 The fullerene derivative of the present invention preferably has 1 to 4 structures represented by the formula (1). From the viewpoint of ease of synthesis, it is more preferable to have one or two structures represented by the formula (1).
本発明のフラーレン誘導体において、Ｃ６０フラーレンの誘導体の具体例としては、下記化合物があげられる。
本発明のフラーレン誘導体において、Ｃ７０フラーレンの誘導体の具体例としては、下記化合物があげられる。
本発明のフラーレン誘導体としては、式（２ａ）又は式（２ｂ）で表されるフラーレン誘導体が好ましい。
[式中、Ａ環は炭素数６０以上のフラーレン骨格を表す。Ｒ及びｒは、前述と同じ意味を表す。]
[式中、Ａ環は炭素数６０以上のフラーレン骨格を表す。Ｒ及びｒは、前述と同じ意味を表す。複数個あるＲは、同一でも相異なってもよい。複数個あるｒは、同一でも相異なってもよい。]
As a fullerene derivative of this invention, the fullerene derivative represented by Formula (2a) or Formula (2b) is preferable.
[In the formula, A ring represents a fullerene skeleton having 60 or more carbon atoms. R and r represent the same meaning as described above. ]
[In the formula, A ring represents a fullerene skeleton having 60 or more carbon atoms. R and r represent the same meaning as described above. A plurality of R may be the same or different. A plurality of r may be the same or different. ]
式（２ａ）及び式（２ｂ）において、原料の入手性の観点からは、Ａ環はＣ60フラーレン、Ｃ70フラーレンであることが好ましい。 In Formula (2a) and Formula (2b), from the viewpoint of availability of raw materials, the A ring is preferably C 60 fullerene or C 70 fullerene.
本発明のフラーレン誘導体を用いて製造した有機光電変換素子は、光電変換効率が高くなる。 The organic photoelectric conversion element manufactured using the fullerene derivative of the present invention has high photoelectric conversion efficiency.
本発明のフラーレン誘導体の合成方法は、例えば、グリシン誘導体とアルデヒド類から生成するイミンから脱炭酸して生じるイミニウムカチオンと、フラーレンとの１，３−双極子環化付加反応(Prato反応、Accounts of Chemical Research Vol.31 1998 519-526ページ)により合成することができる。
ここで用いられるグリシン誘導体としては、Ｎ−メトキシメチルグリシン、Ｎ−(２−（２−メトキシエトキシ）エチル)グリシンなどが例示される。
該グリシン誘導体の使用量は、フラーレン１モルに対して、通常０．１〜１０モル、好ましくは０．５〜３モルの範囲である。
もう一つの原料であるアルデヒド類としては、式（５）で表されるアルデヒドなどが例示される。
該アルデヒド類の使用量は、フラーレン１モルに対して、通常０．１〜１０モル、好ましくは０．５〜４モルの範囲である。
通常、本発明のフラーレン誘導体の合成反応は、溶媒中で行なわれる。該溶媒としては、トルエン、キシレン、ヘキサン、オクタン、クロルベンゼンなど、該合成反応に対して不活性な溶媒が用いられる。該溶媒の使用量は、フラーレンに対して通常１〜１０００００重量倍の範囲である。
反応に際しては、例えば溶媒中でグリシン誘導体とアルデヒド類とフラーレンとを混合し加熱反応させればよく、反応温度は、通常５０〜３５０℃の範囲である。反応時間は、通常、３０分間から５０時間である。
加熱反応後、反応混合物を室温まで放冷し，溶媒をロータリーエバポレーターで減圧留去し、得られた固形物をシリカゲルフラッシュカラムクロマトグラフィーで分離精製して目的とするフラーレン誘導体を得ることができる。
Examples of the glycine derivative used here include N-methoxymethylglycine and N- (2- (2-methoxyethoxy) ethyl) glycine.
The usage-amount of this glycine derivative is 0.1-10 mol normally with respect to 1 mol of fullerene, Preferably it is the range of 0.5-3 mol.
Examples of aldehydes that are another raw material include aldehydes represented by the formula (5).
The amount of the aldehyde used is usually in the range of 0.1 to 10 mol, preferably 0.5 to 4 mol, relative to 1 mol of fullerene.
Usually, the synthesis reaction of the fullerene derivative of the present invention is carried out in a solvent. As the solvent, a solvent inert to the synthesis reaction such as toluene, xylene, hexane, octane, chlorobenzene and the like is used. The amount of the solvent used is usually in the range of 1 to 100000 times the weight of fullerene.
In the reaction, for example, a glycine derivative, an aldehyde, and fullerene may be mixed and heated in a solvent, and the reaction temperature is usually in the range of 50 to 350 ° C. The reaction time is usually 30 minutes to 50 hours.
After the heating reaction, the reaction mixture is allowed to cool to room temperature, the solvent is distilled off under reduced pressure using a rotary evaporator, and the resulting solid is separated and purified by silica gel flash column chromatography to obtain the desired fullerene derivative.
式（１）中に含まれるベンゾシクロブテン基は熱架橋性を有するため、本発明のフラーレン誘導体を加熱して架橋させることができる。有機光電変換素子の熱安定性を増す観点からは、本発明のフラーレン誘導体を加熱して架橋させることが好ましい。 Since the benzocyclobutene group contained in the formula (1) has thermal crosslinkability, the fullerene derivative of the present invention can be crosslinked by heating. From the viewpoint of increasing the thermal stability of the organic photoelectric conversion element, it is preferable to crosslink the fullerene derivative of the present invention by heating.
＜組成物＞
本発明の組成物は、前記フラーレン誘導体と電子供与性化合物とを含む。
<Composition>
The composition of the present invention contains the fullerene derivative and an electron donating compound.
前記電子供与性化合物は、塗布性の観点からは、高分子化合物であることが好ましい。高分子化合物としては、ポリビニルカルバゾール及びその誘導体、ポリシラン及びその誘導体、側鎖又は主鎖に芳香族アミンを有するポリシロキサン誘導体、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体、ポリピロール及びその誘導体、ポリフェニレンビニレン及びその誘導体、ポリチエニレンビニレン及びその誘導体、ポリフルオレン及びその誘導体等が挙げられる。 The electron donating compound is preferably a polymer compound from the viewpoint of coatability. Examples of the polymer compound include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and Examples thereof include polythienylene vinylene and derivatives thereof, polyfluorene and derivatives thereof, and the like.
有機光電変換素子に用いる電子供与性化合物は、変換効率の観点からは、式（１０）及び式（１１）からなる群から選ばれる繰り返し単位を有する高分子化合物であることが好ましく、式（１０）で表される繰り返し単位を有する高分子化合物であることがより好ましい。
（１０） （１１）
[式中、Ｒ6、Ｒ7、Ｒ8、Ｒ9、Ｒ10、Ｒ11、Ｒ12、Ｒ13、Ｒ14及びＲ15は、同一又は相異なり、水素原子、アルキル基、アルコキシ基又はアリール基を表す。]
The electron donating compound used in the organic photoelectric conversion element is preferably a polymer compound having a repeating unit selected from the group consisting of formula (10) and formula (11) from the viewpoint of conversion efficiency. It is more preferable that it is a high molecular compound which has a repeating unit represented by this.
(10) (11)
[Wherein, R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are the same or different and are a hydrogen atom, an alkyl group, an alkoxy group or an aryl group. Represents a group. ]
式（１０）中、Ｒ6及びＲ7がアルキル基である場合の具体例としては、前述のＲの例示と同じアルキル基があげられる。Ｒ6及びＲ7がアルコキシ基である場合の具体例としては、前述のＲの例示と同じアルコキシ基があげられる。Ｒ6及びＲ7がアリール基である場合の具体例としては、前述のＲの例示と同じアリール基があげられる。 In formula (10), specific examples of R 6 and R 7 being an alkyl group include the same alkyl groups as those exemplified above for R. Specific examples where R 6 and R 7 are alkoxy groups include the same alkoxy groups as those exemplified above for R. Specific examples of the case where R 6 and R 7 are aryl groups include the same aryl groups as those exemplified above for R.
式（１０）中、変換効率の観点からは、Ｒ6及びＲ7の少なくとも一方が、炭素数１〜２０のアルキル基であることが好ましく、炭素数４〜８のアルキル基であることがより好ましい。 In formula (10), from the viewpoint of conversion efficiency, at least one of R 6 and R 7 is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 4 to 8 carbon atoms. preferable.
式（１１）中、Ｒ8〜Ｒ15がアルキル基である場合の具体例としては、前述のＲの例示と同じアルキル基があげられる。Ｒ8〜Ｒ15がアルコキシ基である場合の具体例としては、前述のＲの例示と同じアルコキシ基があげられる。Ｒ8〜Ｒ15がアリール基である場合の具体例としては、前述のＲの例示と同じアリール基があげられる。 In formula (11), specific examples of R 8 to R 15 being an alkyl group include the same alkyl groups as those exemplified above for R. Specific examples of the case where R 8 to R 15 are alkoxy groups include the same alkoxy groups as those exemplified above for R. Specific examples when R 8 to R 15 are aryl groups include the same aryl groups as those exemplified above for R.
式（１１）中、モノマーの合成の行いやすさの観点からは、Ｒ10〜Ｒ15は水素原子であることが好ましい。また、変換効率の観点からは、Ｒ8及びＲ9は炭素数１〜２０のアルキル基又は炭素数６〜２０のアリール基であることが好ましく、炭素数５〜８のアルキル基又は炭素数６〜１５のアリール基であることがより好ましい。 In formula (11), R 10 to R 15 are preferably hydrogen atoms from the viewpoint of ease of monomer synthesis. Moreover, from the viewpoint of conversion efficiency, R 8 and R 9 are preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and an alkyl group having 5 to 8 carbon atoms or 6 carbon atoms. More preferred is an aryl group of ˜15.
本発明の組成物に含まれるフラーレン誘導体は、電子供与性化合物１００重量部に対して、１０〜１０００重量部であることが好ましく、５０〜５００重量部であることがより好ましい。 The fullerene derivative contained in the composition of the present invention is preferably 10 to 1000 parts by weight, and more preferably 50 to 500 parts by weight with respect to 100 parts by weight of the electron donating compound.
＜有機光電変換素子＞
本発明の有機光電変換素子は、少なくとも一方が透明又は半透明である一対の電極と、該電極間に本発明に用いられるフラーレン誘導体を含む層を有する。本発明に用いられるフラーレン誘導体は、電子受容性化合物として用いることも電子供与性化合物として用いることもできるが、電子受容性化合物として用いることが好ましい。
<Organic photoelectric conversion element>
The organic photoelectric conversion element of the present invention has a pair of electrodes, at least one of which is transparent or translucent, and a layer containing a fullerene derivative used in the present invention between the electrodes. The fullerene derivative used in the present invention can be used as an electron-accepting compound or an electron-donating compound, but is preferably used as an electron-accepting compound.
次に、有機光電変換素子の動作機構を説明する。透明又は半透明の電極から入射した光エネルギーが電子受容性化合物及び／又は電子供与性化合物で吸収され、電子とホールの結合した励起子を生成する。生成した励起子が移動して、電子受容性化合物と電子供与性化合物が隣接しているヘテロ接合界面に達すると界面でのそれぞれのＨＯＭＯエネルギー及びＬＵＭＯエネルギーの違いにより電子とホールが分離し、独立に動くことができる電荷（電子とホール）が発生する。発生した電荷は、それぞれ電極へ移動することにより外部へ電気エネルギー（電流）として取り出すことができる。 Next, the operation mechanism of the organic photoelectric conversion element will be described. Light energy incident from a transparent or translucent electrode is absorbed by the electron-accepting compound and / or the electron-donating compound to generate excitons in which electrons and holes are combined. When the generated excitons move and reach the heterojunction interface where the electron-accepting compound and the electron-donating compound are adjacent to each other, electrons and holes are separated due to the difference in HOMO energy and LUMO energy at the interface. Electric charges (electrons and holes) that can move are generated. The generated charges can be taken out as electric energy (current) by moving to the electrodes.
本発明の有機光電変換素子の具体的としては、
１．少なくとも一方が透明又は半透明である一対の電極と、該電極間に設けられ電子受容性化合物として本発明のフラーレン誘導体を含有する第一の層と、該第一の層に隣接して設けられた電子供与性化合物を含有する第二の層とを有することを特徴とする有機光電変換素子、
２．少なくとも一方が透明又は半透明である一対の電極と、該電極間に設けられ電子受容性化合物として本発明のフラーレン誘導体及び電子供与性化合物を含有する層を少なくとも一層有することを特徴とする有機光電変換素子、
３．少なくとも一方が透明又は半透明である一対の電極と、該電極間に設けられ本発明のフラーレン誘導体を加熱して架橋させて形成した第一の層と、該第一の層に隣接して設けられた電子供与性化合物を含有する第二の層とを有することを特徴とする有機光電変換素子、
４．少なくとも一方が透明又は半透明である一対の電極と、該電極間に設けられフラーレン誘導体と電子供与性化合物とを含む本発明の組成物を加熱し、該フラーレン誘導体を架橋させて形成した層を少なくとも一層有することを特徴とする有機光電変換素子、
のいずれかが好ましい。
As a specific example of the organic photoelectric conversion element of the present invention,
1. A pair of electrodes, at least one of which is transparent or translucent, a first layer provided between the electrodes and containing the fullerene derivative of the present invention as an electron-accepting compound, and provided adjacent to the first layer An organic photoelectric conversion element comprising a second layer containing an electron donating compound,
2. An organic photoelectric sensor comprising a pair of electrodes, at least one of which is transparent or translucent, and at least one layer provided between the electrodes and containing the fullerene derivative of the present invention and an electron-donating compound as an electron-accepting compound. Conversion element,
3. A pair of electrodes, at least one of which is transparent or translucent, a first layer formed between the electrodes by heating and crosslinking the fullerene derivative of the present invention, and provided adjacent to the first layer An organic photoelectric conversion element comprising a second layer containing the electron donating compound obtained,
4). A layer formed by heating a composition of the present invention comprising a pair of electrodes, at least one of which is transparent or translucent, and a fullerene derivative and an electron donating compound provided between the electrodes, and crosslinking the fullerene derivative. An organic photoelectric conversion element comprising at least one layer,
Either of these is preferable.
ヘテロ接合界面を多く含むという観点からは、前記２の有機光電変換素子が好ましい。また、本発明の有機光電変換素子には、少なくとも一方の電極と本発明に用いられるフラーレン誘導体を含む層との間に付加的な層を設けてもよい。付加的な層としては、例えば、ホール又は電子を輸送する電荷輸送層が挙げられる。 From the viewpoint of including many heterojunction interfaces, the organic photoelectric conversion element of 2 is preferable. Moreover, you may provide an additional layer in the organic photoelectric conversion element of this invention between at least one electrode and the layer containing the fullerene derivative used for this invention. Examples of the additional layer include a charge transport layer that transports holes or electrons.
前記２の有機光電変換素子おいて、フラーレン誘導体及び電子供与性化合物を含有する有機層におけるフラーレン誘導体の割合が、電子供与性化合物１００重量部に対して、１０〜１０００重量部であることが好ましく、５０〜５００重量部であることがより好ましい。 In the organic photoelectric conversion element of 2, the ratio of the fullerene derivative in the organic layer containing the fullerene derivative and the electron donating compound is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the electron donating compound. 50 to 500 parts by weight is more preferable.
前記２の有機光電変換素子おいて、フラーレン誘導体及び電子供与性化合物を含有する有機層は、フラーレン誘導体と電子供与性化合物とを含む組成物を用いて製造することができる。 In the organic photoelectric conversion device of the second aspect, the organic layer containing the fullerene derivative and the electron donating compound can be produced using a composition containing the fullerene derivative and the electron donating compound.
本発明の有機光電変換素子に用いることができるフラーレン誘導体を含む層は、該フラーレン誘導体を含む有機薄膜から形成されていることが好ましい。該有機薄膜の厚さは、通常、１ｎｍ〜１００μｍであり、好ましくは２ｎｍ〜１０００ｎｍであり、より好ましくは５ｎｍ〜５００ｎｍであり、さらに好ましくは２０ｎｍ〜２００ｎｍである。 The layer containing a fullerene derivative that can be used in the organic photoelectric conversion element of the present invention is preferably formed from an organic thin film containing the fullerene derivative. The thickness of the organic thin film is usually 1 nm to 100 μm, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and further preferably 20 nm to 200 nm.
前記３、４の有機光電変換素子に用いられるフラーレン誘導体を架橋させて形成した層の一つの製造方法は、本発明のフラーレン誘導体と溶媒とを含む溶液を一方の電極上（陽極上又は陰極上）に塗布して有機層を形成し、次いで、該有機層を加熱する方法である。また、他の製造方法としては、本発明の組成物と溶媒とを含む溶液を一方の電極上に塗布して有機層を形成し、次いで、該有機層を加熱する方法がある。これらの有機光電変換素子の一態様において、フラーレン誘導体を架橋させて形成した層は活性層として機能する。
フラーレン誘導体を架橋させて形成した層は、架橋したフラーレン誘導体を含む有機薄膜から形成されていてもよい。該有機薄膜の厚さは、通常、１ｎｍ〜１００μｍであり、好ましくは２ｎｍ〜１０００ｎｍであり、より好ましくは５ｎｍ〜５００ｎｍであり、さらに好ましくは２０ｎｍ〜２００ｎｍである。
One method for producing a layer formed by crosslinking a fullerene derivative used in the organic photoelectric conversion elements 3 and 4 described above includes a solution containing the fullerene derivative of the present invention and a solvent on one electrode (on an anode or on a cathode). ) To form an organic layer, and then the organic layer is heated. As another production method, there is a method in which a solution containing the composition of the present invention and a solvent is applied on one electrode to form an organic layer, and then the organic layer is heated. In one embodiment of these organic photoelectric conversion elements, a layer formed by crosslinking a fullerene derivative functions as an active layer.
The layer formed by crosslinking the fullerene derivative may be formed from an organic thin film containing a crosslinked fullerene derivative. The thickness of the organic thin film is usually 1 nm to 100 μm, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and further preferably 20 nm to 200 nm.
本発明の有機光電変換素子は、通常、基板上に形成される。この基板の材料は、電極を形成し、有機物の層を形成する際に化学的に変化しないものであればよい。基板の材料としては、例えば、ガラス、プラスチック、高分子フィルム、シリコン等が挙げられる。不透明な基板の場合には、反対の電極（即ち、基板から遠い方の電極）が透明又は半透明であることが好ましい。 The organic photoelectric conversion element of the present invention is usually formed on a substrate. The material of the substrate may be any material that does not chemically change when the electrode is formed and the organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. In the case of an opaque substrate, the opposite electrode (that is, the electrode far from the substrate) is preferably transparent or translucent.
透明又は半透明の電極の材料としては、導電性の金属酸化物膜、半透明の金属薄膜等が挙げられる。具体的には、酸化インジウム、酸化亜鉛、酸化スズ、及びそれらの複合体であるインジウム・スズ・オキサイド（ＩＴＯ）、インジウム・亜鉛・オキサイド等からなる導電性材料を用いて作製された膜（ＮＥＳＡ等）や、金、白金、銀、銅等が用いられ、ＩＴＯ、インジウム・亜鉛・オキサイド、酸化スズが好ましい。電極の作製方法としては、真空蒸着法、スパッタリング法、イオンプレーティング法、メッキ法等が挙げられる。 また、電極材料として、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体等の有機の透明導電膜を用いてもよい。 Examples of the material for the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film thereof (NESA) manufactured using a conductive material made of indium / tin / oxide (ITO), indium / zinc / oxide, or the like. Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.
電極材料としては、好ましくは一対の電極のうち一方の電極は仕事関数の小さい材料が好ましい。仕事関数の小さい材料を含む電極は、透明又は半透明であってもよい。該材料としては、例えば、リチウム、ナトリウム、カリウム、ルビジウム、セシウム、マグネシウム、カルシウム、ストロンチウム、バリウム、アルミニウム、スカンジウム、バナジウム、亜鉛、イットリウム、インジウム、セリウム、サマリウム、ユーロピウム、テルビウム、イッテルビウム等の金属、及びそれらのうち２つ以上の合金、又はそれらのうち１つ以上と、金、銀、白金、銅、マンガン、チタン、コバルト、ニッケル、タングステン、錫のうち１つ以上との合金、グラファイト又はグラファイト層間化合物が用いられる。合金の例としては、マグネシウム−銀合金、マグネシウム−インジウム合金、マグネシウム−アルミニウム合金、インジウム−銀合金、リチウム−アルミニウム合金、リチウム−マグネシウム合金、リチウム−インジウム合金、カルシウム−アルミニウム合金が挙げられる。 As the electrode material, one of the pair of electrodes is preferably a material having a small work function. An electrode including a material having a low work function may be transparent or translucent. Examples of the material include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like, And alloys of two or more of them, or one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite Intercalation compounds are used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.
電極と本発明に用いられるフラーレン誘導体を含む層との間に設けてもよい付加的な層は、バッファ層であってもよく、バッファ層として用いられる材料としては、フッ化リチウム等のアルカリ金属、アルカリ土類金属のハロゲン化物、酸化チタン等の酸化物等が挙げられる。また、無機半導体を用いる場合、微粒子の形態で用いることもできる。 The additional layer that may be provided between the electrode and the layer containing the fullerene derivative used in the present invention may be a buffer layer. The material used as the buffer layer may be an alkali metal such as lithium fluoride. And alkaline earth metal halides and oxides such as titanium oxide. When an inorganic semiconductor is used, it can be used in the form of fine particles.
＜有機薄膜の製造方法＞
前記有機薄膜の製造方法は、特に制限されず、例えば、本発明に用いられるフラーレン誘導体を含む溶液からの成膜による方法が挙げられる。
<Method for producing organic thin film>
The method for producing the organic thin film is not particularly limited, and examples thereof include a method by film formation from a solution containing the fullerene derivative used in the present invention.
溶液からの成膜に用いる溶媒は、本発明に用いられるフラーレン誘導体を溶解させるものであれば特に制限はない。この溶媒としては、例えば、トルエン、キシレン、メシチレン、テトラリン、デカリン、ビシクロヘキシル、ｎ−ブチルベンゼン、ｓｅｃ−ブチルベゼン、ｔｅｒｔ−ブチルベンゼン等の炭化水素系溶媒、四塩化炭素、クロロホルム、ジクロロメタン、ジクロロエタン、クロロブタン、ブロモブタン、クロロペンタン、ブロモペンタン、クロロヘキサン、ブロモヘキサン、クロロシクロヘキサン、ブロモシクロヘキサン等のハロゲン化飽和炭化水素系溶媒、クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン等のハロゲン化不飽和炭化水素系溶媒、テトラヒドロフラン、テトラヒドロピラン等のエーテル系溶媒が挙げられる。前記フラーレン誘導体は、通常、前記溶媒に０．１重量％以上溶解させることができる。 The solvent used for film formation from a solution is not particularly limited as long as it can dissolve the fullerene derivative used in the present invention. Examples of the solvent include hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbezen, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, Halogenated saturated hydrocarbon solvents such as chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene, tetrahydrofuran And ether solvents such as tetrahydropyran. The fullerene derivative can usually be dissolved in the solvent in an amount of 0.1% by weight or more.
前記溶液は、さらに高分子化合物を含んでいてもよい。該溶液に用いられる溶媒の具体例としては、前述の溶媒があげられるが、高分子化合物の溶解性の観点からは、芳香族の炭化水素系溶媒が好ましく、トルエン、キシレン、メシチレンがより好ましい。 The solution may further contain a polymer compound. Specific examples of the solvent used in the solution include the above-mentioned solvents. From the viewpoint of the solubility of the polymer compound, aromatic hydrocarbon solvents are preferable, and toluene, xylene, and mesitylene are more preferable.
溶液からの成膜には、スピンコート法、キャスティング法、マイクログラビアコート法、グラビアコート法、バーコート法、ロールコート法、ワイアーバーコート法、ディップコート法、スプレーコート法、スクリーン印刷法、フレキソ印刷法、オフセット印刷法、インクジェット印刷法、ディスペンサー印刷法、ノズルコート法、キャピラリーコート法等の塗布法を用いることができ、スピンコート法、フレキソ印刷法、インクジェット印刷法、ディスペンサー印刷法が好ましい。 For film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic method Coating methods such as a printing method, an offset printing method, an ink jet printing method, a dispenser printing method, a nozzle coating method, a capillary coating method can be used, and a spin coating method, a flexographic printing method, an ink jet printing method, and a dispenser printing method are preferable.
有機光電変換素子は、透明又は半透明の電極から太陽光等の光を照射することにより、電極間に光起電力が発生し、有機薄膜太陽電池として動作させることができる。有機薄膜太陽電池を複数集積することにより有機薄膜太陽電池モジュールとして用いることもできる。 By irradiating light such as sunlight from a transparent or translucent electrode, the organic photoelectric conversion element generates a photovoltaic force between the electrodes and can be operated as an organic thin film solar cell. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.
また、電極間に電圧を印加した状態で、透明又は半透明の電極から光を照射することにより、光電流が流れ、有機光センサーとして動作させることができる。有機光センサーを複数集積することにより有機イメージセンサーとして用いることもできる。 In addition, by applying light from a transparent or translucent electrode in a state where a voltage is applied between the electrodes, a photocurrent flows and it can be operated as an organic photosensor. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.
以下、本発明をさらに詳細に説明するために実施例を示すが、本発明はこれらに限定されるものではない。 Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
合成に用いた試薬及び溶媒は、市販品をそのまま使用するか、乾燥剤存在下で蒸留精製した品を使用した。Ｃ60フラーレンはフロンティアカーボン社製を使用した。ＮＭＲスペクトルはＪＥＯＬ社製 ＭＨ５００を用いて測定し、テトラメチルシラン（ＴＭＳ）を内部標準に使用した。赤外吸収スペクトルは島津製作所社製 ＦＴ−ＩＲ ８０００を用いて測定した。 ＭＡＬＤＩ−ＴＯＦ ＭＳスペクトルはＢＲＵＫＥＲ社製 ＡｕｔｏＦＬＥＸ−Ｔ２を用いて測定した。 As reagents and solvents used in the synthesis, commercially available products were used as they were or products obtained by distillation purification in the presence of a desiccant were used. C 60 fullerene was manufactured by Frontier Carbon. The NMR spectrum was measured using MH500 manufactured by JEOL, and tetramethylsilane (TMS) was used as an internal standard. The infrared absorption spectrum was measured using FT-IR 8000 manufactured by Shimadzu Corporation. The MALDI-TOF MS spectrum was measured using an AutoFLEX-T2 manufactured by BRUKER.
実施例１（フラーレン誘導体Ａの合成）
（ベンジル[２−（２−ヒドロキシエトキシ）エチルアミノ]アセテートの合成）
(Synthesis of benzyl [2- (2-hydroxyethoxy) ethylamino] acetate)
Ｒｆ ０．７１（ヘキサン／エチルアセテート＝４／１）;
１Ｈ ＮＭＲ（５００ＭＨｚ,ｐｐｍ,ＣＤＣｌ３) δ 3.81 (s, 2H), 5.14 (s, 2H), 7.31 (s, 5H);
１３Ｃ ＮＭＲ（１２５ＭＨｚ，ｐｐｍ，ＣＤＣｌ３） δ 25.74, 67.79, 128.27, 128.48, 128.54, 134.88, 166.91;
ＩＲ（ｎｅａｔ,ｃｍ−１) 2959, 1751, 1458, 1412, 1377, 1167, 972, 750, 698。
R f 0.71 (hexane / ethyl acetate = 4/1);
1 H NMR (500 MHz, ppm, CDCl 3 ) δ 3.81 (s, 2H), 5.14 (s, 2H), 7.31 (s, 5H);
13 C NMR (125 MHz, ppm, CDCl 3 ) δ 25.74, 67.79, 128.27, 128.48, 128.54, 134.88, 166.91;
IR (neat, cm −1 ) 2959, 1751, 1458, 1412, 1377, 1167, 972, 750, 698.
［第２ステップ］: アルゴン雰囲気下、ブロモ酢酸ベンジルエステル（１３．７ｇ、６０ｍｍｏｌ）のジクロロメタン（９０ｍＬ）溶液にトリエチルアミン（１７ｍＬ、１２０ｍｍｏｌ）を０℃で加え、得られた混合液を２０分同温度で攪拌し、ついで、２−（２−アミノエトキシ）エタノール（１２ｍＬ、１２０ｍｍｏｌ）のジクロロメタン（４０ｍＬ）溶液を加え、室温で４時間攪拌した。ついで、有機層を水洗（３回）後，無水硫酸マグネシウムで乾燥し、エバポレーターで溶媒を減圧留去後、シリカゲルフラッシュカラムクロマトグラフィー（展開溶媒：酢酸エチル／メタノール＝１／０、１０／１、５／１）で精製し、グリシンエステル２（１２．２ｇ、４８．０ｍｍｏｌ）を収率８０％で無色油状物として得た。 [Second Step]: Under an argon atmosphere, triethylamine (17 mL, 120 mmol) was added at 0 ° C. to a solution of benzyl bromoacetate (13.7 g, 60 mmol) in dichloromethane (90 mL), and the resulting mixture was kept at the same temperature for 20 minutes. Then, a solution of 2- (2-aminoethoxy) ethanol (12 mL, 120 mmol) in dichloromethane (40 mL) was added, and the mixture was stirred at room temperature for 4 hours. Next, the organic layer was washed with water (3 times), dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure with an evaporator, and silica gel flash column chromatography (developing solvent: ethyl acetate / methanol = 1/0, 10/1, 5/1) to obtain glycine ester 2 (12.2 g, 48.0 mmol) as a colorless oil in a yield of 80%.
Ｒｆ ０．４８（エチルアセテート／メタノール＝２／１）;
１Ｈ ＮＭＲ（５００ＭＨｚ,ｐｐｍ,ＣＤＣｌ３） δ 2.83 (t, 2H, Ｊ＝５．１Ｈｚ), 3.50 (s, 2H), 3.52 (t, 2H, Ｊ＝４．６Ｈｚ), 3.58 (t, 2H, Ｊ＝５．０Ｈｚ), 3.65 (t, 2H, Ｊ＝４．６Ｈｚ), 5.11 (s, 2H), 7.28-7.30 (m, 5H);
１３Ｃ ＮＭＲ（１２５ＭＨｚ，ｐｐｍ，ＣＤＣｌ３） δ 48.46, 50.25, 61.29, 66.38, 69.80, 72.23, 126.63, 128.12, 128.37, 135.30, 171.78;
ＩＲ（ｎｅａｔ,ｃｍ−１) 3412, 2880, 1719, 1638, 1560, 1508, 1458, 1067, 669。
R f 0.48 (ethyl acetate / methanol = 2/1);
1 H NMR (500 MHz, ppm, CDCl 3 ) δ 2.83 (t, 2H, J = 5.1 Hz), 3.50 (s, 2H), 3.52 (t, 2H, J = 4.6 Hz), 3.58 (t, 2H , J = 5.0 Hz), 3.65 (t, 2H, J = 4.6 Hz), 5.11 (s, 2H), 7.28-7.30 (m, 5H);
13 C NMR (125 MHz, ppm, CDCl 3 ) δ 48.46, 50.25, 61.29, 66.38, 69.80, 72.23, 126.63, 128.12, 128.37, 135.30, 171.78;
IR (neat, cm −1 ) 3412, 2880, 1719, 1638, 1560, 1508, 1458, 1067, 669.
（[２−（２−メトキシエトキシ）エチルアミノ]酢酸(１)の合成）
Rf 0.58（エチルアセテート／メタノール＝２０／１）;
1H NMR (500 MHz, ppm, CDCl3) δ 1.34 (d, 9H, Ｊ＝54.5 Hz), 2.19 (brs, 1H), 3.38-3.45 (m, 4H), 3.50-3.60 (m, 4H), 3.99 (d, 2H, Ｊ＝41.3 Hz), 5.09 (d, 2H, Ｊ＝4.1 Hz), 7.25-7.30 (m, 5H);
13C NMR (125 MHz, ppm, CDCl3) δ 27.82, 28.05, 47.90, 48.20, 49.81, 50.39, 61.23, 66.42, 69.92, 72.12, 80.08, 127.93, 128.14, 135.25, 154.99, 155.19, 169.94, 170.07;
IR (neat, cm-1) 3449, 2934, 2872, 1751, 1701, 1458, 1400, 1367, 1252, 1143;
Anal. Calcd for C18H27NO6: C, 61.17; H, 7.70; N, 3.96. Found: C, 60.01; H, 7.75; N, 4.13。
R f 0.58 (ethyl acetate / methanol = 20/1);
1 H NMR (500 MHz, ppm, CDCl 3 ) δ 1.34 (d, 9H, J = 54.5 Hz), 2.19 (brs, 1H), 3.38-3.45 (m, 4H), 3.50-3.60 (m, 4H), 3.99 (d, 2H, J = 41.3 Hz), 5.09 (d, 2H, J = 4.1 Hz), 7.25-7.30 (m, 5H);
13 C NMR (125 MHz, ppm, CDCl 3 ) δ 27.82, 28.05, 47.90, 48.20, 49.81, 50.39, 61.23, 66.42, 69.92, 72.12, 80.08, 127.93, 128.14, 135.25, 154.99, 155.19, 169.94, 170.07;
IR (neat, cm -1 ) 3449, 2934, 2872, 1751, 1701, 1458, 1400, 1367, 1252, 1143;
. Anal Calcd for C 18 H 27 NO 6:. C, 61.17; H, 7.70; N, 3.96 Found: C, 60.01; H, 7.75; N, 4.13.
［第２ステップ］: アルゴンガス雰囲気下，水素化ナトリウム（１．２ｇ、２４．８ｍｍｏｌ、５０％ ｉｎ ｍｅｎｅｒａｌ ｏｉｌ）のテトラヒドロフラン（ＴＨＦ）（１０ｍＬ）溶液にベンジル｛ｔｅｒｔ−ブトキシカルボニル−［２−（２−ヒドロキシ−エトキシ）エチル］アミノ｝アセテート（５．８３ｇ、１６．５ｍｍｏｌ）のＴＨＦ（２０ｍＬ）溶液を０℃で滴下し、同温度で２０分攪拌後、ヨードメタン（１．６ｍＬ、２４．８ｍｍｏｌ）を０℃で加えた。 反応混合液を室温で２０時間攪拌し、ついでアイスバスで冷却しながら水を加えて反応を停止した．エーテル抽出（３回）し、有機層を乾燥後、減圧濃縮、シリカゲルフラッシュカラムクロマトグラフィー（展開溶媒：ヘキサン／酢酸エチル＝５／１、３／１）で精製して ベンジル｛ｔｅｒｔ−ブトキシカルボニル−［２−（２−メトキシ−エトキシ）エチル］アミノ｝アセテート（３．０２ｇ、８．２１ｍｍｏｌ）を収率５０％で無色油状物として得た。 [Second Step]: Sodium hydride (1.2 g, 24.8 mmol, 50% in general oil) in tetrahydrofuran (THF) (10 mL) in an argon gas atmosphere was added to benzyl {tert-butoxycarbonyl- [2- ( 2-Hydroxy-ethoxy) ethyl] amino} acetate (5.83 g, 16.5 mmol) in THF (20 mL) was added dropwise at 0 ° C. and stirred at the same temperature for 20 minutes, and then iodomethane (1.6 mL, 24.8 mmol). ) Was added at 0 ° C. The reaction mixture was stirred at room temperature for 20 hours, and then water was added while cooling with an ice bath to stop the reaction. After extraction with ether (3 times), the organic layer was dried, concentrated under reduced pressure, and purified by silica gel flash column chromatography (developing solvent: hexane / ethyl acetate = 5/1, 3/1) to obtain benzyl {tert-butoxycarbonyl- [2- (2-Methoxy-ethoxy) ethyl] amino} acetate (3.02 g, 8.21 mmol) was obtained as a colorless oil in a yield of 50%.
Rf 0.54（ヘキサン／エチルアセテート＝１／１）;
1H NMR (500 MHz, ppm, CDCl3) δ 1.34 (d, 9H, Ｊ＝51.8 Hz), 3.28 (d, 3H, Ｊ＝2.7 Hz), 3.37-3.46 (m, 6H), 3.52 (dt, 2H, Ｊ＝5.4Hz, 16.5 Hz), 4.02 (d, 2H, J= 34.8 Hz), 5.09 (d, 2H, J=4.5 Hz), 7.24-7.30 (m, 5H);
13C NMR (125 MHz, ppm, CDCl3) δ 24.93, 25.16, 44.68, 45.00, 46.70, 47.40, 55.78, 63.30, 67.22, 68.60, 76.95, 124.98, 125.14, 125.36, 132.49, 151.99, 152.31, 166.84, 166.96;
IR (neat, cm-1) 2880, 1751, 1701, 1560, 1458, 1400, 1366, 1117, 698, 617;
Anal. Calcd for C19H29NO6: C, 62.11; H, 7.96; N, 3.81. Found: C, 62.15; H, 8.16; N, 3.83。
R f 0.54 (hexane / ethyl acetate = 1/1);
1 H NMR (500 MHz, ppm, CDCl 3 ) δ 1.34 (d, 9H, J = 51.8 Hz), 3.28 (d, 3H, J = 2.7 Hz), 3.37-3.46 (m, 6H), 3.52 (dt, 2H, J = 5.4Hz, 16.5 Hz), 4.02 (d, 2H, J = 34.8 Hz), 5.09 (d, 2H, J = 4.5 Hz), 7.24-7.30 (m, 5H);
13 C NMR (125 MHz, ppm, CDCl 3 ) δ 24.93, 25.16, 44.68, 45.00, 46.70, 47.40, 55.78, 63.30, 67.22, 68.60, 76.95, 124.98, 125.14, 125.36, 132.49, 151.99, 152.31, 166.84, 166.96 ;
IR (neat, cm -1 ) 2880, 1751, 1701, 1560, 1458, 1400, 1366, 1117, 698, 617;
Anal. Calcd for C 19 H 29 NO 6 : C, 62.11; H, 7.96; N, 3.81. Found: C, 62.15; H, 8.16; N, 3.83.
［第３ステップ］: アルゴン雰囲気下、ベンジル｛ｔｅｒｔ−ブトキシカルボニル−［２−（２−メトキシ−エトキシ）エチル］アミノ｝アセテート（３．０２ｇ、８．２１ｍｍｏｌ）のジクロロメタン（１７ｍＬ）溶液にトリフルオロ酢酸（ＴＦＡ）（９．０ｍＬ）を加え室温で7時間攪拌した。ついで、１０％炭酸ナトリウム水溶液を加えて ｐＨ１０に調整し、ジクロロメタン抽出し、有機層を無水硫酸マグネシウムで乾燥し、減圧濃縮してベンジル［２−（２−メトキシ−エトキシ）エチルアミノ］アセテート（２．１８ｇ、８．１９ｍｍｏｌ）を黄色油状物として定量的に得た。 [Third Step]: Trifluoromethane in a solution of benzyl {tert-butoxycarbonyl- [2- (2-methoxy-ethoxy) ethyl] amino} acetate (3.02 g, 8.21 mmol) in dichloromethane (17 mL) under an argon atmosphere. Acetic acid (TFA) (9.0 mL) was added and stirred at room temperature for 7 hours. Subsequently, 10% aqueous sodium carbonate solution was added to adjust the pH to 10, followed by extraction with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and benzyl [2- (2-methoxy-ethoxy) ethylamino] acetate (2 .18 g, 8.19 mmol) was obtained quantitatively as a yellow oil.
Rf 0.32 （エチルアセテート／メタノール＝２０／１）;
1H NMR (500 MHz, ppm, CDCl3) δ 1.99 (brs, 1H), 2.83 (t, 2H, Ｊ＝5.3 Hz), 3.38 (s, 3H), 3.50 (s, 2H), 3.54 (t, 2H, Ｊ＝4.6 Hz), 3.60-3.62 (m, 4H), 5.17 (s, 2H), 7.32-7.38 (m, 5H);
13C NMR (125 MHz, ppm, CDCl3) δ 48.46, 50.66, 58.76, 66.20, 70.00, 70.44, 71.64, 128.09, 128.33, 135.44, 171.84;
IR (neat, cm-1) 3350, 2876, 1736, 1560, 1458, 1117, 1030, 698, 619;
Anal. Calcd for C14H21NO4: C, 62.90; H, 7.92; N, 5.24. Found: C, 62.28; H, 8.20; N, 5.05。
R f 0.32 (ethyl acetate / methanol = 20/1);
1 H NMR (500 MHz, ppm, CDCl 3 ) δ 1.99 (brs, 1H), 2.83 (t, 2H, J = 5.3 Hz), 3.38 (s, 3H), 3.50 (s, 2H), 3.54 (t, 2H, J = 4.6 Hz), 3.60-3.62 (m, 4H), 5.17 (s, 2H), 7.32-7.38 (m, 5H);
13 C NMR (125 MHz, ppm, CDCl 3 ) δ 48.46, 50.66, 58.76, 66.20, 70.00, 70.44, 71.64, 128.09, 128.33, 135.44, 171.84;
IR (neat, cm -1 ) 3350, 2876, 1736, 1560, 1458, 1117, 1030, 698, 619;
Anal. Calcd for C 14 H 21 NO 4 : C, 62.90; H, 7.92; N, 5.24. Found: C, 62.28; H, 8.20; N, 5.05.
［第４ステップ］: ベンジル［２−（２−メトキシ−エトキシ）エチルアミノ］アセテート（２．１９ｇ、８．１９ｍｍｏｌ）のメタノール（２７ｍＬ）溶液に、パラジウムを１０重量％担持させた活性炭（２１９ｍｇ）を室温で加え、水素ガスをパージした後、水素雰囲気下、室温で７時間攪拌した。セライトパッドをしきつめたグラスフィルターでＰｄ／Ｃを除去し、セライト層をメタノールで洗浄し、濾液を減圧濃縮し[２−（２−メトキシエトキシ）エチルアミノ]酢酸 1（１．３８ｇ、７．７８ｍｍｏｌ）を収率９５％で黄色油状物として得た。 [Step 4]: Activated carbon (219 mg) in which palladium is supported on 10% by weight of a solution of benzyl [2- (2-methoxy-ethoxy) ethylamino] acetate (2.19 g, 8.19 mmol) in methanol (27 mL). Was purged with hydrogen gas at room temperature, and then stirred at room temperature for 7 hours under a hydrogen atmosphere. Pd / C was removed with a glass filter with a celite pad, the celite layer was washed with methanol, the filtrate was concentrated under reduced pressure, and [2- (2-methoxyethoxy) ethylamino] acetic acid 1 (1.38 g, 7.78 mmol). ) Was obtained in 95% yield as a yellow oil.
1H NMR (500 MHz, ppm, MeOD) δ 3.21 (t, 2H, Ｊ＝5.1 Hz), 3.38 (s, 3H), 3.51 (s, 2H), 3.57 (t, 2H, Ｊ＝4.4 Hz), 3.65 (t, 2H, Ｊ＝4.6 Hz), 3.73 (t, 2H, Ｊ＝5.1 Hz);
13C NMR (125 MHz, ppm, MeOD) δ 48.13, 50.49, 59.16, 67.08, 71.05, 72.85, 171.10;
IR (neat, cm-1) 3414, 2827, 1751, 1630, 1369, 1111, 1028, 851, 799;
Anal. Calcd for C7H15NO4: C, 47.45; H, 8.53; N, 7.90. Found: C, 46.20; H, 8.49; N, 7.43。
1 H NMR (500 MHz, ppm, MeOD) δ 3.21 (t, 2H, J = 5.1 Hz), 3.38 (s, 3H), 3.51 (s, 2H), 3.57 (t, 2H, J = 4.4 Hz), 3.65 (t, 2H, J = 4.6 Hz), 3.73 (t, 2H, J = 5.1 Hz);
13 C NMR (125 MHz, ppm, MeOD) δ 48.13, 50.49, 59.16, 67.08, 71.05, 72.85, 171.10;
IR (neat, cm -1 ) 3414, 2827, 1751, 1630, 1369, 1111, 1028, 851, 799;
. Anal Calcd for C 7 H 15 NO 4:. C, 47.45; H, 8.53; N, 7.90 Found: C, 46.20; H, 8.49; N, 7.43.
アルデヒド類４の合成
窒素雰囲気下、５０ｍｌナスフラスコにブロモ体 ３ ３．０ｇ（１６．３ｍｍｏｌ）、無水テトラヒドロフラン（ＴＨＦ）５０ｍｌを仕込み、窒素気流下−７８℃に冷却し、ｎ−ブチルリチウムヘキサン溶液（１．５９Ｍ）１１．３ｍｌ（１８．０ｍｍｏｌ）を滴下し、同温度で３０分撹拌した。次いで、ナスフラスコ中に無水ジメチルホルムアミド２．４０ｇを滴下し、同温度でさらに３０分攪拌した後、室温まで昇温し、さらに１時間攪拌した。反応液を水１００ｍｌ中に注ぎ、酢酸エチル５０ｍｌを用いて油相を２回抽出した後、無水硫酸マグネシウムを用いて油相を乾燥した。マグネシウム化合物を濾別後、エバポレータを用いて油相を減圧濃縮し得られた残渣を、シリカゲルクロマトグラフィー（ＷａｋｏｓｉｌＣ−３００、展開液：ヘキサン／酢酸エチル＝３：１（容積比））にて精製することで、目的物であるアルデヒド類 ４を１．５４ｇ（収率７１．１％）得た。
Synthesis of aldehydes 4
Under a nitrogen atmosphere, 3.0 g (16.3 mmol) of bromo 3 and 50 ml of anhydrous tetrahydrofuran (THF) were charged in a 50 ml eggplant flask, cooled to −78 ° C. under a nitrogen stream, and an n-butyllithium hexane solution (1.59 M). 11.3 ml (18.0 mmol) was added dropwise and stirred at the same temperature for 30 minutes. Next, 2.40 g of anhydrous dimethylformamide was dropped into the eggplant flask, and the mixture was further stirred at the same temperature for 30 minutes, then warmed to room temperature and further stirred for 1 hour. The reaction solution was poured into 100 ml of water, the oil phase was extracted twice with 50 ml of ethyl acetate, and then the oil phase was dried with anhydrous magnesium sulfate. After the magnesium compound is filtered off, the residue obtained by concentrating the oil phase under reduced pressure using an evaporator is purified by silica gel chromatography (Wakosil C-300, developing solution: hexane / ethyl acetate = 3: 1 (volume ratio)). As a result, 1.54 g (yield: 71.1%) of the target aldehyde 4 was obtained.
1Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ3）：
δ３．２４（ｓ、４H）、７．２１（ｄ、１Ｈ）、７．５７（ｓ、１H）、７．７２（ｄ、１Ｈ）、９．９３（ｓ、１Ｈ）
1 H-NMR (270 MHz / CDCl 3 ):
δ 3.24 (s, 4H), 7.21 (d, 1H), 7.57 (s, 1H), 7.72 (d, 1H), 9.93 (s, 1H)
実施例１
フラーレン誘導体Ａ及びフラーレン誘導体Ｂの合成
窒素雰囲気下、５０ｍｌナスフラスコにアルデヒド類 ４ ０．１９ｇ（１．４０ｍｍｏｌ）とグリシン誘導体 １ ０．１９ｇ（１．０４ｍｍｏｌ）、Ｃ６０ ０．５０ｇ（０．６９ｍｍｏｌ）、クロロベンゼン３０ｍｌを仕込み、窒素気流下１３０℃にて６時間加熱撹拌した。反応液を室温まで冷却後、反応液をエバポレータを用いて減圧濃縮した。次いで、シリカゲルクロマトグラフィー（ＷａｋｏｓｉｌＣ−３００）を用いて、得られた残渣からフラーレン誘導体の分離を行った。フラーレン誘導体の分離において、シリカゲルクロマトグラフィーの展開液として、二硫化炭素（ＣＳ２）を用い、未反応のＣ６０を分離し、回収した。次いで、展開液をトルエンと酢酸エチルの混合溶媒に切り替え、混合溶媒の比率を１００：０（トルエンと酢酸エチルの体積比）から９０：１０（トルエンと酢酸エチルの体積比）とし、フラーレン誘導体を含む結晶を分離した。該結晶をメタノール１０ｍｌで洗浄し、減圧乾燥することで目的物である５（フラーレン誘導体Ａ）を８０ｍｇ（収率１１．９％）得た。
次いで、展開液の混合溶媒の比率をトルエン／酢酸エチル＝１：１（体積比）として分画を行った。分画した溶液を濃縮し、残渣をメタノール１０ｍｌで洗浄し、その後、減圧乾燥することで、式（１２）で表される構造を２個以上有するフラーレン誘導体を合計１１６ｍｇ得た。式（１２）で表される構造を２個以上有するフラーレン誘導体としては、例えば、６（フラーレン誘導体Ｂ）が挙げられる。
Synthesis of fullerene derivative A and fullerene derivative B
Under a nitrogen atmosphere, 0.19 g (1.40 mmol) of aldehyde 4, 0.19 g (1.04 mmol) of glycine derivative 1, 0.50 g (0.69 mmol) of C60, and 30 ml of chlorobenzene and 30 ml of chlorobenzene were charged in a nitrogen stream. The mixture was heated and stirred at 130 ° C. for 6 hours. After cooling the reaction solution to room temperature, the reaction solution was concentrated under reduced pressure using an evaporator. Subsequently, the fullerene derivative was separated from the obtained residue using silica gel chromatography (Wakosil C-300). In the separation of the fullerene derivative, carbon disulfide (CS 2 ) was used as a developing solution for silica gel chromatography, and unreacted C60 was separated and recovered. Next, the developing solution was switched to a mixed solvent of toluene and ethyl acetate, the ratio of the mixed solvent was changed from 100: 0 (volume ratio of toluene and ethyl acetate) to 90:10 (volume ratio of toluene and ethyl acetate), and the fullerene derivative was changed to The containing crystals were separated. The crystals were washed with 10 ml of methanol and dried under reduced pressure to obtain 80 mg (yield 11.9%) of the target product 5 (fullerene derivative A).
Next, fractionation was performed with the ratio of the mixed solvent of the developing solution being toluene / ethyl acetate = 1: 1 (volume ratio). The fractionated solution was concentrated, and the residue was washed with 10 ml of methanol and then dried under reduced pressure to obtain a total of 116 mg of fullerene derivatives having two or more structures represented by formula (12). Examples of the fullerene derivative having two or more structures represented by the formula (12) include 6 (fullerene derivative B).
フラーレン誘導体ＡをＮＭＲで分析した結果を以下に示す。
1Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ３）：
δ２．８２（ｍ、１Ｈ）、３．１６（ｂｒｓ、４Ｈ）、３．３０−３．５０（ｍ、１Ｈ）、３．４５（ｓ、３Ｈ）３．６５（ｍ、２Ｈ）、３．７２−３．８０（ｍ、２Ｈ）、３．９０−４．１０（ｍ、２Ｈ）、４．２８（ｄ、１Ｈ）、５．１０（ｓ、１Ｈ）、５．２０（ｄ、１Ｈ）、７．０６（ｄ、１Ｈ）、７．４０―７．７０（ｂｒｄ、１Ｈ）。
The result of analyzing fullerene derivative A by NMR is shown below.
1 H-NMR (270 MHz / CDCl 3 ):
δ 2.82 (m, 1H), 3.16 (brs, 4H), 3.30-3.50 (m, 1H), 3.45 (s, 3H) 3.65 (m, 2H), 3. 72-3.80 (m, 2H), 3.90-4.10 (m, 2H), 4.28 (d, 1H), 5.10 (s, 1H), 5.20 (d, 1H) 7.06 (d, 1H), 7.40-7.70 (brd, 1H).
実施例２
（有機薄膜太陽電池の作製、評価）
電子供与体としてレジオレギュラーポリ３−ヘキシルチオフェン（アルドリッチ社製、ロット番号：０９００７ＫＨ）を１％（重量％）の濃度でクロロベンゼンに溶解させた。その後、フラーレン誘導体Ａを電子供与体の重量に対して等倍重量となるように電子受容体として溶液に混合した。ついで、孔径１．０μｍのテフロン（登録商標）フィルターで濾過し、塗布溶液を作製した。
Example 2
(Production and evaluation of organic thin-film solar cells)
Regioregular poly-3-hexylthiophene (manufactured by Aldrich, lot number: 09007 KH) as an electron donor was dissolved in chlorobenzene at a concentration of 1% (weight%). Thereafter, the fullerene derivative A was mixed into the solution as an electron acceptor so as to have an equal weight with respect to the weight of the electron donor. Subsequently, it filtered with the Teflon (trademark) filter with the hole diameter of 1.0 micrometer, and produced the application | coating solution.
スパッタ法により１５０ｎｍの厚みでＩＴＯ膜を付けたガラス基板をオゾンＵＶ処理して表面処理を行った。次に、前記塗布溶液を用い、スピンコートにより塗布し、有機薄膜太陽電池の活性層（膜厚約１００ｎｍ）を得た。その後、窒素雰囲気下１３０℃の条件で１０分間ベークを行った。その後、真空蒸着機によりフッ化リチウムを４ｎｍの厚さで蒸着し、次いでＡｌを１００ｎｍの厚さで蒸着した。蒸着のときの真空度は、すべて１〜９×１０-3Ｐａであった。また、得られた有機薄膜太陽電池の形状は、２ｍｍ×２ｍｍの正四角形であった。得られた有機薄膜太陽電池の開放端電圧、光電変換効率は、ソーラシミュレーター(分光計器製、商品名OTENTO-SUNII：AM1.5Gフィルター、放射照度100mW/cm2)を用いて一定の光を照射し、発生する電流と電圧を測定して求めた。開放端電圧の結果を表１に示す。また、光電変換効率は３．０％であった。 A glass substrate provided with an ITO film with a thickness of 150 nm by a sputtering method was subjected to surface treatment by ozone UV treatment. Next, the coating solution was applied by spin coating to obtain an active layer (film thickness of about 100 nm) of the organic thin film solar cell. Thereafter, baking was performed for 10 minutes under a condition of 130 ° C. in a nitrogen atmosphere. Then, lithium fluoride was vapor-deposited with a thickness of 4 nm by a vacuum vapor deposition machine, and then Al was vapor-deposited with a thickness of 100 nm. The degree of vacuum at the time of vapor deposition was 1 to 9 × 10 −3 Pa in all cases. Moreover, the shape of the obtained organic thin-film solar cell was a regular square of 2 mm × 2 mm. The open-circuit voltage and photoelectric conversion efficiency of the obtained organic thin-film solar cells were irradiated with constant light using a solar simulator (trade name OTENTO-SUNII: AM1.5G filter, irradiance 100 mW / cm 2 ). The generated current and voltage were measured and obtained. Table 1 shows the results of the open-circuit voltage. The photoelectric conversion efficiency was 3.0%.
実施例３
（有機薄膜太陽電池の作製、評価）
実施例２におけるフラーレン誘導体Ａを実施例１で製造した式（１２）で表される構造を２個以上有するフラーレン誘導体にかえた以外は実施例２と同様の操作を行い、開放端電圧を測定した。結果を表１に示す。
Example 3
(Production and evaluation of organic thin-film solar cells)
The open circuit voltage was measured in the same manner as in Example 2 except that the fullerene derivative A in Example 2 was replaced with a fullerene derivative having two or more structures represented by the formula (12) produced in Example 1. did. The results are shown in Table 1.
比較例１
（有機薄膜太陽電池の作製、評価）
実施例２におけるフラーレン誘導体Ａを[６０]−ＰＣＢＭ(Phenyl C61-butyric acid methyl ester、フロンティアカーボン社製、商品名Ｅ１００、ロット番号：９Ａ０１０４Ａ)にかえた以外は実施例２と同様の操作を行い、開放端電圧を測定した。開放端電圧の結果を表１に示す。また、光電変換効率は２．６％であった。
Comparative Example 1
(Production and evaluation of organic thin-film solar cells)
The same operation as in Example 2 was performed except that the fullerene derivative A in Example 2 was changed to [60] -PCBM (Phenyl C61-butyric acid methyl ester, manufactured by Frontier Carbon Co., Ltd., trade name E100, lot number: 9A0104A). The open circuit voltage was measured. Table 1 shows the results of the open-circuit voltage. The photoelectric conversion efficiency was 2.6%.
Claims (9)
[式中、Ｒは１価の有機基を表す。ｒは０〜４の整数を表す。] The fullerene derivative which has a structure represented by Formula (1).
[Wherein, R represents a monovalent organic group. r represents an integer of 0 to 4. ]
[式中、Ａ環は炭素数６０以上のフラーレン骨格を表す。Ｒ及びｒは、前述と同じ意味を表す。]
[式中、Ａ環は炭素数６０以上のフラーレン骨格を表す。Ｒ及びｒは、前述と同じ意味を表す。複数個あるＲは、同一でも相異なってもよい。複数個あるｒは、同一でも相異なってもよい。] The fullerene derivative of Claim 1 or 2 represented by Formula (2a) or Formula (2b).
[In the formula, A ring represents a fullerene skeleton having 60 or more carbon atoms. R and r represent the same meaning as described above. ]
[In the formula, A ring represents a fullerene skeleton having 60 or more carbon atoms. R and r represent the same meaning as described above. A plurality of R may be the same or different. A plurality of r may be the same or different. ]
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